Malting process



3,086,921 MALTKNG PRUCESS John G. Fleckenstein, Broohfield, Wis, assignor to Kurth Melting Company, Milwaukee, Wis, a corporation of Wisconsin No Drawing. Filed Sept. 12, 1961, Ser. No. 137,525 Claims. (Cl. res-4e This invention relates to the production of malt. More particularly, this invention is concerned with a novel method of producing malt in which enzyme production, especially the alpha-amylase content, is stimulated and the modification of the malt is increased.

Many compounds have been found to effect cereal seed germination and modification. Some of them stimulate, while others retard growth and modification of the resulting malt. One stimulatory material in common use is gibberellic acid which stimulates growth and enzymatic development of the germinating cereal grain. This enhancement of growth and enzymatic development is important to the maltster, since these malts are preferred for some uses over malts that are prepared without added gibberellic acid. Gibberellic acid though is an expensive product isolated from the metabolic products of certain mold species. To be entirely suitable cheaper, and more readily obtainable, compounds which give the desired results are needed. t

It has been found, according to the present invention, that certain O-phenyl phosphates and O-phenyl phosphorothioates act during the germination of a grain being malted to increase the enzymatic potential and modification of the resulting malt.

The O-phenyl phosphates and O-phenyl phosphorothioates which have been found to have this ability may be represented by the formulas l antas.

and

wherein R is a member of the group consisting oi} lower alkyls such as methyl, ethyl, propyl and isopropyl and aralkyl groups such as phenyl-lower alkyl groups including benzyl and phenethyl, R is a member of the group wherein R and R are the same or different groups in- 3,8,2l Patented Apr. 23, 1963 eluding hydrogen, alkyls such as methyl, ethyl, propyl, isopropyl and octyl, phenyl-alkyl groups such as benzyl and phenethyl, and R represents from 1 to 5, and advisably 1 to 3, nuclear substituents on the phenyl group taken from the group consisting of hydrogen, hydroxy, halogens and particularly chlorine and bromine, lower alkyl groups such as methyl and ethyl, lower alkoxy groups such as methoxy and ethoxy and nitro.

Of the described compounds, those which appear to increase the enzymatic potential and modification of the malt most are those of the formulas in which R has the assigned meaning, R is a lower alkyl and particularly is methyl and R is hydrogen or a lower alkyl such as methyl and isopropyl. Furthermore, of the groups represented by R the evidence indicates that halogens and particularly chlorine in the 2,4 and 3,4-positions of the phenyl ring have the greatest activity.

The compounds with which this invention is concerned are shown in the prior art, as for example, United States Patent No. 2,552,574.

Some specific O-phenyl phosphates and O-phenyl phosphorothioates which can be used in practicing the invention are:

0-(4-chlorophenyl)-O-methyl phosphor-amidothioate,

O-( 3,4-dichlorophenyl) -O-methyl isopropylphosphoramidothioate,

0,0-dimethy-l-O- (2,4-dichlorophenyl -phosphorothio ate,

0-(2,4-dichlorophenyl)-O-methyl phosphoramidothioate,

O-(2,4,5-trichlorophenyl)-O-methyl dimethylphosphoramidothioate,

O-(2,4,5-trichlorophenyl)-O-isopropyl octylphosphoramidothioate,

O-(2-chloro-4-tert-butylphenyl)-O-methyl methylphosphorarnidoate,

O-(2,4-dichlorophenyl)-0,0-dimethyl phosphate,

O-(2,4-dichlorophenyl)-O-methyl ethylphosphoramidoate,

O-(2,4-dichlorophenyl)-O-butyl isopropylphosphor amidoate,

O-(2,4,5-trichlorophenyl)-O-methyl phosphoramidoate,

O-'(2,4,5-trichlorophenyl)-O-methyl dimethylphosphoramidoate,

0- 2,4,5-trichlorophenyl -O-methyl octylphosphoramidoate and O-(3-nitrophenyl)-O-benzyl benzylphosphoramidothioate.

The O-phenyl phosphates and O-phenyl phosphorothioates have been found to selectively stimulate the formation of alpha-amylase and the breakdown of the starch matrix, or modification, of the endosperm during the germination process. They do not appear to have any effect on other physical or chemical properties of the 4 EXAMPLE 1 350 grams of Kindred barley was weighed into a one-'; gallon bottle and steeped at 55 F. with appropriate water 1 a1 changes. Water was added to the steeped barley to 1.651 ant m 1 5 bring the moisture pickup to 200 gm. The compound In order to fifiect the i Eng/me sumu anon 01.16 being tested was dissolved in 5 ml. of acetone and the or m of thesqcompounds apphefi cereal f solution added to the steeped barley. The barley wasdurmg the maltmg piocess and 'advlsably m the penod germinated for five days at 63-65 F. under controlled from Steep R to passage of more than 50% conditions of agitation, ventilation and humidity. of the germmailon lume- P however mhe best After germination the green malts were kilned 12 hours i l by aPPlYmg The to the at 120 F., 4 hours at 140 F., 6 hours at 160 F. and gram 1n the period [from steep out to the end of the first 2 hours at F. day of germination. It is believed feasible, nevertheless, The a1pha amy1ase values for the malts were deter to Include mhe compouflds m the Steep Water durmg the mined according to the method in Methods of Analysis last day or so of steepmg' 15 of the American Society of Brewing Chemists, 6th ed, V g amounts of F requlred, page 169 (1958), American Society of Brewing Chemwith as little as 1 part per million by weight and usually ists, Madison 5 Wisconsin. no more than 500 parts per million, based on t e Welght The modification index of each sample was determined. of cemal gram Put to steep? P Sultable most of It is a measure of the conversion of the barley, or other the compounds. Concentrataion levels 0t 5 to 200 parts grain, to malt. The higher the value, the greater is the Per Infill-0n are Suitable for most although conversion into malt. The modification index determinaamounts of from to 75 Parts Per mflhon of r tion provides similar information as is furnished by the P Y l normally to assure Obtammg the Wort viscosity and coarse-fine difference determinations. enzymatic increase and avoiding possible adverse effects. It is to be understood that variation in activities of the 25 M difi ti compounds exists, and, therefore, the optimum amount TCA Vlscoslty for Specific compound can be detel'mined y Simple Trichloroacetic acid viscosity is determined as follows: screening tests. A 25 gm. sample of malt is finely ground (Miag Cone These compounds are usually applied to the cereal Mill, setting 95). A flask is heated to approximately 68 grain after s eping by di per ing hem in a ui able 0 C., 25 mls. of 40% trichloroacetic acid added and then carrier to obtain a more satisfactory volume to dosage 200 mm, of hot tap water. The mixture is cooled to ratio. 68 C., the 25 gm. of malt added and the mixture Some of the compounds are water insoluble oils, and ble ded 2 minutes and filtered. others are water insoluble solids. However, they are A isc simeter is cooled to 20 C. and a 10 ml. sample sollb1e in the wmmon Organic Solvents 511011 a8 2106- 5 of the malt dispersion is added. After cooling to 20 C. 31601101, bfiflzene, heXalle- The Solution the running time is recorded. This is then repeated. sultingcan then be diluted with water using a suitable The water time of the viscosimeter is measured by ep m q emulslfying agent s n sary to m adding 10 ml. of distilled water to a clean, drained vis, tam p rslon of the compound In the q P Y- cosimeter and the running time measured at 20 C. ing or sprinkling can then be used to apply the dispersion 40 Th i it i th l lated as follows: to the grain.

The practice of this invention does not require changes TCA i it l f malt solution in the other steps of the malting process. Conventional Runmng mm of Water steeping, germination and kilning schedules can be used. Control samples were also run and alpha-amylase val- The malt recoveries are about the same or slightly higher ues of 40-45 obtained while the modification index values than those obtained without the use of the phosphates, for the controls were from 25 to 30.

This invention is useful in the malting of cereal grains, The compounds tested and the results obtained are rein addition to barley, including Wheat, rice, oats and rye. ported in Tables 1 and 2. The values are reported as in- The following example illustrates the practice of this creases over the values obtained for the controls run invention. simultaneously.

Table 1 Ri fi/Rg @K Alpha-Amylase Increase/Modification Index Increase, Treatment Level, ppm. NO R1 R2 R3 4-chlor0 -NH1 5/14 4-ch10ro -NHCH (OHM- 1/12 3,4-dichloro- -NHCH(CHa)2 2,4-dichlor0l OOH;; 2,4-dichloro NH2 6/17 2,4-dichlor0 HCzH 2,4-diehlor0 NHOH(CH3)2 5/4 2,4-di0hl0l0 I z a a 2,4-diohloro NHCH(CH3)1 2,4-dichloro. -NH CH (CH3)2 2,4,5-trichl0ro. -O CH; 2,4,5-trichl0r0. NH2 2,4,5-trichloro N (CHM 2,4,5-trichl0ro NHOH(GH3)2 2,4,5-trichlor0 NH(CH2)1OH 16 2,4,5trlchl0r0 -OOH(OH3) NHCH(CHa)z Table 2 R1 fi/Rg Alpha-Amylase Increase/Modification Index Increase, Treatment Level, ppm.

No. R1 Ra Rs 17 4-telr1t-buty1-2- OOH NHOH; -l22 1/31 9/28 0 oro.

l8 2,4-dichloro OCH3- 0OH 7/18 8/26 6/26 9/22 -10/17 19. 2,4dichloro OCHa NH; 4/10 /22 19/28 21/31 29/23 11/27 20 2,4-dichloro OCH3- NHCH(CH:):---- 6/21 20/28 21/30 21/30 32/28 6/28 21 2,4,5-t1'ichl0ro- OOH NH --2/ -/15 9/7 22- 2,4,5-trichloro.-- OCHa -NHOH(CH 4/16 10119 10/12 Various changes and modifications of the invention can be made and, to the extent that such variations incorporate the spirit of this invention, they are intended to be included within the scope of the appended claims.

What is claimed is:

1. The process of malting in which grain is subjected, in the period consisting of the malting steps of steeping and germination of the steeped grain to the action of a compound of the formula in R2 wherein Z is a member of the group consisting of oxygen and sulfur, R is a member of the group consisting of lower alkyl and phenyl-lower alkyl, R is a member of the group consisting of lower alkoxy, phenyl-lower alkoxy and groups in which R represents groups of the formula wherein R and R are members of the group consisting of hydrogen, lower alkyl and phenyl-lower alkyl and R represents from =1 to 5 nuclear substituents on the phenyl group selected from the group consisting of hydrogen, hydroxy, halogen, lower alkyl, lower alkoxy and nitro.

2. The process of claim 1 in which 1 to 500 parts per million of the compound, based on the weight of grain put to steep, is used.

3. The process of claim 1 in which the grain is barley.

4. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of a compound of the formula l r R:

wherein R and R are members of the group consisting of hydrogen, lower alkyl and phenyl-lower alkyl, and R represents from 1 to 5 nuclear substituents on the phenyl group selected from the group consisting of hydrogen,

hydroxy, halogen, lower alkyl, lower alkoxy and nitro to a steeped cereal grain and then germinating and drying the grain.

5. The process of claim 4 in which the grain is barley.

6. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of O-(2,4-dichlorophenyl)-O-methyl phosphoramidothioate to a steeped cereal grain and then germinating and drying the grain.

7. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of O-(3,4dichlorophenyl)-O-methyl isopropylphosphoramidotbioate to a steeped cereal grain and then germinating and drying the gram.

8. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of O-(2,4-dichlorophenyl)-0,0-dimethyl phosphate to a steeped cereal grain and then germinating and drying the grain.

9. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of O-(2,4,5trichlorophenyl)-O-methyl phosphoramidoate to a steeped cereal grain and then germinating and drying the grain.

10. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of O-(2,4,5-trichlorophenyl)-O-methyl phosphoramidothioate to a steeped cereal grain and then germinating and drying the grain.

11. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of O-(2,4-dichlorophenyl)-O-methyl phosphoramidoate to a steeped cereal grain and then germinating and drying the grain.

12. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of O-(2,4-dichlorophenyl)-O-methyl isopropylphosphoramidothioate to a steeped cereal grain and then germinating and drying the gram.

13. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of O-(4-chloropheny1)- O-methyl phosphoramidothioate to a steeped cereal grain and then germinating and drying the grain.

14. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of O-(2,4-dichlorophenyl)-O-methyl ethylphosphoramidoate to a steeped cereal grain and then germinating and drying the grain.

15. The process of increasing the alpha-amylase and modification index values of a malted cereal grain which comprises applying 1 to 500 parts per million, based on the weight of grain put to steep, of O-(2,4-dichlorophenyl) O methyl isopropylphosphoramidoate to a steeped cereal grain and then germinating and drying the grain.

References Cited in the file of this patent UNITED STATES PATENTS Great Britain Aug. 21, 1957 

1. THE PROCESS OF MALTING IN WHICH GRAIN IS SUBJECTED, IN THE PERIOD CONSISTING OF THE MALTING STEPS OF STEEPING AND GERMINATION OF THE STEEPED GRAIN TO THE ACTION OF A COMPOUND OF THE FORMULA 